Method of producing alkali metal titanium fluorides in which the titanium has a valence of less than four



; :iproc'esses and as a result, such compounds are tally great commercial importance.

METHOD OF PRODUCING ALKALI METAL TITA- NIUM FLUORIDES IN WHICH THE TITANIUM HAS A VALENCE F LESS THAN FOUR Quentin H. McKenna, Cleveland, Ohio, assignor, by mesne assignments, to Horizons Titanium Corporation, Princeton, N. J., a corporation of New Jersey No Drawing. Application September 14, 1955, Serial No. 534,403 5 Claims. (CI. 23-88) 1 This invention relates to the preparation of complex i alkali metal-titanium-fluorine compounds in which the titanium has a valence of less than four.

Titanium halides, in which the titanium is divalent or trivalent, are becoming increasingly useful for the proof poten- Various procedures ave been-,suggested for preparing lower valent titanium- '''alkali metal fluorides, including one described in a copending application, Serial No. 455,068, filed September 9, 1954, now United States Patent 2,723,182, which issued November 8, 1955 to Merle E. Sibert and the present applicant. In that application, there is described a process for preparing the desired compounds by a simple thermal reaction between any of the oxides of titanium, carbon and an alkali metal fluotitanate. According to the process therein disclosed, a mixture of the reactants is heated to a temperature within the range of about 780 C. to about 1150 phere, whereby an alkali metal-titanium double fluoride is formed in which the titanium has a valence of less than four.

titanium material. from the process disclosed in the aboveidentified application, inthat it may be efiFected in the absence of carbon.

reactants. prefer, to carry out the reaction at ateminsure that at leastone form; This is particularly advantageous in modifications of my process in which an alkali metal halide, usually the chloride, is present in the reaction mixture as a diluent salt; In such; processes the reaction is effected in a molten saljt environment with many accompanying advantages, particularly when one or more of the reactants dissolves in the diluent salt bath. Regardless of the reactants employed, one of the products formed as a result of the reaction is an alkali metal-titanium double fluoride in which the titanium has a valence less than four. This product" may be recovered from the reaction residue either by aqueous separation or in the form of a molten bath containing the reduced valence compound.

The alkali metal fiuotitanates useful in the practice of my invention include sodium fiuotitanate, potassium fiuotitanate and lithium fluotitan-ate. In order to avoid undesirable side reactions and possible contamination of the product the fiuotitanate employed should be of recrystallized quality. That is to say, the fiuotitanate should be substantially free of silica The instant process difiers principally and metallic impurities C. under an inert atmos-.

and should contain less than about .0l% water and .01% insolubles. Because of the relative cheapness and availability of potassium fluotitanate, I presently prefer to use this fluotitanate in my process. Therefore, in the interest of simplicity, the invention will be described in connection with the use of potassium fluotitanate as a representative of all metal alkali fluotitanates. However, it should be kept in mind thatwhat is said with respect to potassium fluotitanate applies equally to the other alkali metal fluotitanates.

The second reactant in my process is an oxygen containing titanium material, such as one of the oxides of titanium. The oxides I have successfully employed include titanium sesquioxide and titanium monoxide, and other oxides in which the titanium has a valence less than four would appear to be equally suitable. Whatever the oxygen containing titanium material chosen for reaction, it should be very finely divided. Oxides in the form of particles of about minus 325 mesh (Tyler Standard) are preferred, and should be as free as possible from elements other than titanium and oxygen. Silica and metallic impurities which dissolve in potassium fluotitanate, are particularly objectionable in carrying out my process. The preparation of other oxides of suitable purity are described in U. S. Patents 2,681,849, 2,681,850 and 2,681,851.

The reaction between the titanium oxide and the potassium fluotitanate is effected by heating the reactants together in an atmosphere which is inert with respect to the reactants to an elevated temperature below that at which the resulting lower valent complex titanium products decompose or disproportionate. The reaction will proceed to some extent at temperatures well below the melting point of pure potassium fluotitanate (772 C.) and is accelerated with increasing temperature. At temperatures of about 1200 C. or higher, excessive decomposition and disproportionation occur. perature within the range of about 700 C. to about 1150 C. and preferably within the range of about 780 to 1100 C. is Within this range temperatures between about 780 C. and 900 C. promote the formation of a product in which the titanium is trivalent while temperatures above 900 C. favor the formation of products in which the titanium is divalent.

I have observed that if a melt of sodium chloride is prepared by heating the pure salt in a suitable container and either a suitable oxide of titanium or in alkali metal fluotitanate is added to the molten salt, it dissolves gradually, on continued heating without any apparent reaction. However, when both the oxide of titanium and the alkali metal fluotitanate are added to a fused melt of sodium chloride, or when one is added to a salt melt containing the other, a vigorous eifervescence accompanies the gradual disappearance of the added solids and on continued heating, the clear or water white melt is observed to acquire a tint varying from salmon pink to violet, depending on the relative proportions of the constituents and the reaction conditions. While I do not wish to be bound by any particular theory, it my belief that a reaction between the oxygen containing titanium cornpound andthe alkali-metal fluotitanate may occur along one or more of the following lines: 1

Accordingly, a tempreferred in the practice of my invention The reactions postulated in Equations 1, 2, and 6 are favored by lower temperatures while those of Equations 3, 4, 7 and 8 are favored by higher temperatures. It is also considered possible .that a :simple or complex oxyfluoride may form which, under the conditionsof the system, decomposes to yield oxygen and fluorine. I have observed, in addition to the effervescent bubbling of the reactants, that a pungent gas with many of the characteristics of fluorine is evolved from the reactionmass.

In order'for the reaction to proceed efficiently, .it is preferable that .the oxygencontaining titanium material and the alkali metal fluotitanatezshould.intimately contact each other. To this end, they are provided in finely divided form and :are brought together in a suitable reaction vessel. The reaction vessel .is advantageously a graphite.- crucible .orsome similar container that is inert to the reactants atthe :temperatures encountered in the process. The reactants may be premixed in any desired proportionsand added .in solid form to the reaction vessel; or the lower melting reactant, the fluotitanate, may be melted and then the .oxideadded to the melt; or, in cases where afused-carrier saltis employed, a melt of one or more alkali metal .halides maybe prepared'in the vessel and the reactants added thereto. Regardless of themanner of charging, it is necessary that the reaction be conducted under an inert atmosphere.

Any suitable furnace may be .used for carrying out my process, provided it is constructed so that an inert atmosphere can be maintained in the furnace. One such furnace, as described in the earlierfiled application, comprises a steelpot having an-open top which can be sealed with a gas tight lid. Advantageously the steel pot is internallyinsulated with a refractory silicious powder held in place against the walls of the pot by meansof a graphite liner. Air-internal heating element is provided, advantageously comprisinga graphite resistance element adapted to surround the graphite reaction vessel. The graphite reaction vessel containing the reactants is disposed within the graphite resistance element which, in turn, is centrally positioned inthe insulated pot. The necessary electrical connections to the heating element, and the necessary valves and inlet and outlet pipes for the establishment. of the inertatmosphere within the'furnace, are provided in the gastight lid of the steel pot.

To establish an inert atmosphere in the furnace, I presently prefer first to evacuate all of the air from within the furnace, and then to introduce dry argon gas into the furnace, repeating the cycle of evacuation of the atmosphere and replacement with argon gas at least two times. After flushing'out the interior of the furnace in this manner, a flow of dry pure argon gas into and out of the furnace is established inorder to sweep from the atmosphere in thefurnace any gaseous products evolved from the reactants in the course of the reaction.

The reactants are heated in an inert atmosphere. A

furnace such as that described is used to bring the rea'ctants up to a reaction temperature within the range of about"700 to 1150 C. The reactants are held at this reaction temperature for a period of time sufficient to insure that the reaction has gone as close to theoretical completion as the reaction conditions permit. The time required for substantial completion of the reaction depends upon the-intimacy of contact if the reactants are in the-solid state as well as upon the temperature of the reactants. Areaction time of from five to ten hours is usually sufficient for either solid state or fused salt reaction to be completed.

On completion of the reaction, the furnace is allowed to cool and the solidified salt cake is recovered from the crucible removed therefrom. The solidified salt cake recovered from the crucible is reddish brown to greyish lavender incolor and may contain, besides the lower valent titaniu'm -flu'orides' produced by the. reaction, any unreacted ititanium oxide or" titanium scrap, unreduced normal potassium fluoti'tanate, diluent alkali'metal chlorides and any oxyfluorides that may have formed and not have decomposed in the course of the reaction. The lower valent titanium fluoride product can be recovered from the reaction residue by wet chemical treatment or by filtration of the molten salt mass to remove insolubles.

The recovery of the lower valent titanium productby aqueous procedures 'is limited in practice to trivalent titanium fluorides. The'product salt cake is first crushed to a fine powder and then is leached with cold dilute hydrochloricacid to dissolve the complex potassium salts of lower valenttitaniumfluorideswhich are soluble therein, leaving undissolvedanyresidual titanium oxide, potassium fluotitanate and oxyfluorides. A clear green liquor (characteristic of trivalent titanium solutions) is obtained as the result of the leaching operation, and this liquor is thereupon filteredto remove all insoluble: matter. A saturated solution of sodium fluorideis added to the green filtrate while stirring the filtrate until the color changes permanently from green to brownish violet. The solution is then warmed gently, (i. e. toa temperature crystals precipitate out of the colored supernatant liquid. The precipitated crystal are recovered'by filtering the liquid, andthe violet filtrat is again treated with a saturated solution of sodiumffluoride. Upon addition of the sodium fluoride solution with stirring, the violet solution gradually becomes substantially colorless at which point a slight turbidity develops. Gentle warming causes tannish violet colored crystals toprecipitate from the solution leaving a water white supernatantliquid. The secondbatch of precipitated crystals are recovered-by filtration and both batches are then-washed with distilled water and dried at 105 C.

Although the exact structures ofthe complex lower valent titanium fluorides are not known with certainty, it has been found that the sodium fluoride derivatives obained as the first and second precipitates from the green liquor have completely different X-ray patterns, apparently indicative of different sodium fluoride and potassium fluoride contents. However, irrespective of their precise structure, the lower valent titanium fluoride products obtained by the practice of our invention are free from potassium fiuotitanate, and normal sodium and potassium fluorides and chlorides. These reduced titanium products are therefore available for subsequent use in a highly pure state.

When the lower valent titanium fluoride product is recovered by filtration of the fused reactionresidue, the fused salt mass is filtered through a porous graphite or carbon filter, thus separating the molten salt from any residual titanium scrap, fluorides. The resulting fused salt may then be used directly or in mixture with additional diluent alkali metal chlorides in electrolytic processes for the productioufof titanium metal. The'fused salt bath filtration procedure is particularly valuable in the preparation of divalent titanium fluorides, or mixtures of divalent and trivalent titanium fluorides. Divalent titanium fluoride is not generally amenable to aqueous treatment due to the strong reducing properties of divalent titanium salts. Heavy titanium oxide and oxy-y losses in yield can be expected even in highly buffered solutions. Accordingly it'is preferable to recover the titanium difluoride containing product in theform of a fused salt bath in which the divalent titanium is present either in simple or complex difluoride compounds.

The titanium difluoride and trifiuoride products of the process are useful for a variety of purposes including commercially important processes for the preparation of titanium metal.

The following examples are illustrative but not limita tive of .thepractice of my invention:

" Example I A 'rnixture'was formed of pure titanium --mo'noxideand recrystallizedpotassium fluotitanate in the proporof about 40 to C.), whereupon tannish lavender solution leaving .a violeg ture of between 970 C. and 980 C. in an inert atmosphere furnace, in which a continuously changing argon atmosphere had been established. The reaction temperature was maintained for approximately three hours,

whereupon the furnace was permitted to cool. The charge was actually at a temperature above 800 C. for a total of hours including the heating up and cooling down periods. The resulting salt product was a salt cake of a dark purplish color varying between purplish brown and purplish black. During the heating a pungent gas was evolved which contained fluorine.

The salt product was crushed and a representative sample was removed for further examination and analysis. The remainder of the salt product was dissolved in fused sodium chloride and electrolyzed in an inert atmosphere cell constructed as described in U. S. Patent 2,707,170. There resulted a cathode deposit of titanium metal of satisfactory commercial quality.

The salt product preserved for examination and analysis was found to contain over 25% titanium and was found to be free of any unreacted titanium monoxide. The initial titanium content of the KzTiFs was about 20%. Thus the titanium content of the product is indicative of conversion to the compound KTiF3 (Equation 8).

It will be understood that any unreacted starting materials can be separated and recycled if desired and that the salt products may be processed to recover the several constituents separately, as described in copending application Serial No. 455,068 now United States Patent 2,723,182.

I claim:

1. The method of producing alkali-metal-titanium double fluorides in which the titanium has a valence of less than four which comprises: forming a charge consisting essentially of 1) an alkali-metal-titanium fluoride in which the titanium is tetravalent and (2) an oxide or" titanium in which the titanium has a valence of less than four, in which the relative proportions of said alkalimetal titanium double fluoride and said titanium oxide are such as to provide at least one atom of lower valent titanium as oxide for each two atoms of tetravalent titanium as double fluoride; heating the charge to a temperature sufficient to melt at least one of said charge constituents and within the range of 700 C. to 1150* C. Q under an, atmosphere inert with respect to said reactants,

and recovering from the reaction mass at least one resultingalkali-metal double fluoride in which the titanium has a valence of less than four.

2. The method of producing alkali-metal-titanium double fluorides in which the titanium has a valence of three which comprises: forming a charge consisting essenti lly of (1) an alkali-metal-titanium fluoride in which the titanium is tetravalent and (2) an oxide of titanium -in which the titanium has a valence of less than four in which the relative proportions of said alkali-metal-titanium double fluoride and said titanium oxide are such as to provide at least one atom of lower valent titanium as oxide for each two atoms of tetravalent titanium as double fluoride, heating the charge to a temperature sufficient to melt at least one of said charge constituents and within the range of 700 C. to 900 C. under an atmosphere inert with respect to said reactants, and recovering from the reaction mass at least one resulting alkali-metal double fluoride in which the titanium has a valence of three.

3. The method of producing alkali-metal-titanium double fluorides in which the titanium. has a valence of two which comprises: forming a charge consisting essentially of (1) an alkali-metal-titanium fluoride in which the titanium is tetravalent and (2) an oxide of titanium in which the titanium has a valence of less than four in which the relative proportions of said alkali-metal-titanium double fluoride and said titanium oxide are such as to provide at least one atom of lower valent titanium as oxide for each two atoms of tetravalent titanium as double fluoride, heating the charge to a temperature sufficient to melt at least one of said charge constituents and within the range of 900 C. to 1150 C. under an atmosphere inert with respect to said reactants, and recovering from the reaction mass at least one resulting alkali-metaldouble flouride in which the titanium has a valence of two.

4. The method of producing alkali metal titanium double fluorides in which the titanium has a valence less than four which comprises: forming a charge consisting of an alkali metal titanium double fluoride in which the titanium is tetravalent and titanium monoxide, the molar proportion of titanium monoxide to the alkali metal double fluoride in said charge being at least 1:2, heating the charge to a temperature within the range 700 C. to 1150 C. under an atmosphere inert with respect to said reactants and recovering from the reaction mass at least one resulting alkali metal titanium double fluoride in which the titanium has a valence of less than four.

5. The method of producing alkali metal titanium double fluorides in which the titanium has a valence less than four which comprises: forming a charge consisting of an alkali metal titanium double fluoride in which the titanium is tetravalent and titanium sesquioxide, the molar proportion of titanium sesquioxide to the alkali metal double fluoride in said charge being at least 1:4, heating the charge to a temperature within the range 700 C. to 1150 C. under an atmosphere inert with respect to said reactants and recovering from the reaction mass at least one resulting alkali metal titanium double fluoride in which the titanium has a valence of less than four.

Gross et al Sept. 20, 1955 Sibert et a1 Nov. 8, 1955 

1. THE METHOD OF PRODUCING ALKALI-TITANIUM DOUBLE FLUORIDES IN WHICH THE TITANIUM HAS A VALENCE OF LESS THEN FOUR WHICH COMPRISES: FORMING A CHARGE CONSISTING ESSENTIALLY OF (1) AN ALKALI-METAL-TITANIUM FLUORIDE IN WHICH THE TITANIUM IS TETRAVALENT AND (2) AN OXIDE OF TITANIUM IN WHICH THE TITANIUM HS A VALENCE OF LESS THAN FOUR, IN WHICH THE RELATIVE PROPORTIONS OF SAID ALKALIMETAL TITANIUM DOUBLE FLUORIDE AND SAID TITANIUM OXIDE AE SUCH AS TO PROVIDE AT LEAST ONE ATOM OF LOWER VALENT TITANIUM AS OXIDE FOR EACH TWO ATOMS OF TETRAVALENT TITANIUM AS DOUBLE FLUORIDE; HEATING THE CHARGE TO A TEMPERATURE SUFFICIENT OT MELT AT LEAST ONE OF SAID CHARGE CONSTITUENTS AND WITHIN THE RANGE OF 700*C. TO 1150*C. UNDER AN ATMOSPHERE INERT WITH RESPECT TO SAID REACTANTS, AND RECOVERING FROM THE REACTION MASS AT LEAST ONE RESULTING ALKALI-METAL DOUBLE FLUORIDE IN WHICH THE TITANIUM HAS A VALENCE OF LESS THAN FOUR. 